Pooley won Olympic silver in the road time trial in Beijing
Olympic silver medallist Emma Pooley scored a solo victory over fellow Briton Nicole Cooke at the women's Fleche Wallonne race in Belgium.
The Cervelo rider, who won last year's women's Tour de France, came home eight seconds clear of second-placed Cooke with Sweden's Emma Johans third.
Marianne Vos, who had won the race on the last three occasions, was sixth.
Cadel Evans won the men's race from Joaquim Rodriguez after reeling in an attack from Spain's Alberto Contador.
Bradley Wiggins finished one minute and seven seconds behind in 67th for British-based Team Sky, with Sweden's Thomas Lofkvist the team's highest-placed rider in 23rd over the 123-mile course.
Wiggins had missed the first of the Ardennes Classics, the Amstel Gold race, because of travel disruption caused by the volcanic eruption in Iceland.
Pooley's result moves her up to fourth in the overall World Cup standings after four of nine rounds.
The 27-year-old from Norfolk powered away to victory as the field climbed the steepest section of the Mur de Huy for a second and final time.
"I went a bit early, and I had a gap but you never know," she told Cycling Weekly.
"It is only three hundred metres from there but it feels like miles.
"I would not have won today if all my other team-mates had not been so tired from chasing down the breaks
"Really it was them who won the race!"
Sharon Laws, the only other Briton in the women's race, finished 11th with Stephen Cummings and Chris Froome 74th and 119th respectively on a poor day for Team Sky.
Team Sky aim to win the Tour de France within five years and make their debut in the world famous race this year.